Halogenation products of 1,1-diphenyl-2,2-dimethyl-propane



Patented June 9, 1953 UNITED STATES PATENT OFFICE HALOGENATION PRODUCTS OF 1,1-DI- PHENYL-2,2-DIMETH YL-PROPANE Edward F. Rogers, Middletown, and Horace'D. Brown, Plainficld, N. J assignors-to Merck & 00., Inc., Rahway, N. J., a corporation of New.

' Jersey No Drawing. Application February 16,1950, I

Serial No. 144,593

3 Claims. 1

This invention relates to the new chemical compositions, the halogenation products of .1,1- diphenyl-2,2-dimethylpropane, more particularly the reaction products of the chlorination or bromination of 1,1-diphenyl-2,2-dimeth;yl propane under conditions favoring ring substitution and to the processes for preparing the same.

utilize as starting material 1.,1-diphenyl -2,2-di-" methyl-propane having the formula:

prepared may be used directly or, if desired, more active fractions may be preparedby purification procedures such as fractional distillation.

Also, new insecticidal compositions are pre-"- pared by incorporating in an inert diluentcarrier the reaction products of thechlorination and the bromination of 1,1-dipheny1-2,2-dimethyl-propane under conditions favoring ring substitution, These compounds may be successfully incorporated in a suitable inert solvent or mixture of solvents, or in a solid mixture, with or without other substances, such as wetting, dispersing, and sticking agents. The compounds may be employed in such compositions either as the sole toxic agent or in combination .with other insecticides, such as pyrethrum, rotenone, copper, salts, etc, or with fungicidal or bactericidal;

agents, to-provide compositions useful for household and agricultural dusts and sprays, textile coating and impregnation, and the like. -;For example, we have found that these new compounds are highly soluble in various hydrocar- $113 H CC H acid such as ethyl pivalate with phenyl magnesium bromide to form 1,1-dipheny1-2,2-dimethyl-propanol-l and reacting the latter com: pound with hydrogen in the presence of a copper chromite catalyst. This process and the product thus obtained are fully disclosed and claimed in our copending application Serial No. 144,592, filed February 16,- 1950.

The 1,1-diphenyl-2,2-dimethy1-propane prepared in the above manner is reacted with chlorine or bromine under conditions favoring ring substitution, i. e., in the presence of a catalyst such as iron, at arelatively low temperature, and in the absence of light. The reaction is carried out in a halogenationsolvent such as chloroform or carbon tetrachloride. It is ordinarily preferred to limit the halogenation to that corresponding to di-substitution, as the products obtained in this manner have a high order of insecticidal activity and are at the same time low in halogen content. The reaction products thus bon mixtures, in alcohols, in halogenated hydrocarbons, and the like, and that these compounds may be dissolved in such liquids to provide solutions of enhanced utility. The new compounds may also be placed. in aqueous suspension by dispersing organic solvent solutions of the com pounds in water. Very useful compositions are obtained by mixingithe newcompounds with an inert, finely-divided, solid diluent or carrier, such as bentonite, bole, talc; charcoal, pumice, cal- 1,-1-diphenyl-2,2-dimethyl propane may be prepared by reacting an alkyl ester of pivalic cium carbonate, and'the like. The insecticidal compounds may beadmixed in the original form or in solution. In the latter case, the solvent is expelled to leave the inert solid coated and imforegoing compositions possess excellent stability,

1 no reduction in activity being apparent even after long periods of storage, and are very effective in -destroying injurious insects of all kinds, such as fpreparing these compounds, and thatthey-are;

moths, mosquitoes, flies, beetles, and others.

The preparation of "our novel 'chemical com pounds possessing pronounced insecticidal ao-f tivity may be illustrated by the following specific examples.

tive of the methods and procedures utilized in not intended to berestrictive or to be regarded as embodying the only way in which our novel 5 compounds can be formed and recovered.

' EXAMPLE 1 It should be noted, .of course; that these examples are intended to be illustra-- low the surface of the liquid over a 3.5 hour period, essentially in the absence of light. Hydrothis time. After addition of the bromine was complete, the material was stirred and heated for an additional 2 hours at 70 C. After standing overnight at room temperature, the product was washed with 2.5 N NaOI-I and dried over anhydrous NAzSOi. Evaporation of the. solvent resulted in a yield of 17.2 g. of the bromination product of 1,1-diphenyl-2,2-dimethyl-propane in the form of a crude oil. A portion of the oil was distilled to give the following fractions:

(1) Boiling. point 150-164 C. at about -1 mm.

(2) Boiling point 164-167 C. at 1 mm. (4.0 a),

(3) Boiling point 183-187 C. at 1'mm. (5.0 g.),

Analysis calculated for: CmHisBrz: C, 53.43; H, 4.75; Br, 41.83; found for ,(2): C, 62.78; H, 6.29, Br, 32.53; found for (3): C, 55.45; H, 5.25; Br, 40.80.

EXAMPLE 2 1,1-diphenyl-2,2-dimethyl-propane (45 g.) was dissolved in 150 cc. of carbon tetrachloride and placed in a flask. One gram of iron powder was added and the solution was treatedwith chlorine at -5 C., essentially in the absence of light. After 3 hours the increase in weight corresponded to a di-substitution. At this point chlorine treatment was stopped, the reaction flask was packed in ice and slowly allowed to warm up to room temperature overnight. The product was gen bromide evolution was continuous durin 4 oil was distilled at 1 mm. to give the following fractions:

(1) Boiling point ISO-167 C. (16.2 g.); (2) Boiling point 167-169? C. (20.2 g) V I (3) Boiling point 174-187" C. (8.6 .g.).

Analysis calculated for CrzHmCiz: C, 69.63; H, 6.19; cl, 24.18; found for (1): C, 68.40; H, 5.76; cl, 24.58; found for (2): C, 68.23; H, 5.96; Cl, 27.99; found for (3): C, 63.82; H, 5.55; Cl, 32.23.

EXANEPLE 3 The products prepared as described in EX- amples 1 and 2 were tested for insecticidal activity as follows:

Clothes moth and carpet beetle tests The test method employed was that described by R. E. Heal in a paper entitled Evaluating Protection of Fabrics from Clothes Moth and Carpet Beetle Attack (J. Econ. Ent, 35, (2),, 249-252 (1942)). F q

Woolen fabric was impregnated with acetone solutions of the products to give known concen! trations on the fabric. After evaporation of the solvent, 10 larvae of the Webbing clothes moth Tineola bz'ssellzelia (Hum) or of the blaclz carpet beetle (Attagenus piceus (Oliv.)) were confined on weighed patches of the treated fabric.

for 2 weeks. After removal of the larvae the patches were again weighed. The loss in weight of the fabric is indicated as damage in the table below. Weight loss greater than 10 mgm. is considered to be inadequate protection.

cockroach and millcweed bug tests ure ofF. C. Nelson et 2.1., as described in a paper entitled, Evaluating Liquid'lnsecticides (Soap,

Adults of the German cockroach (Blattella germam'ca (L.)) or of the milkweed bu (Oncopeltus fasci tus (Dallas)) were anaeswashed with dilute sulfuric acid, 5% sodium bithetized with carbon dioxide, and measured carbonate and driedove'ranhydrous sodium sulquantities of acetone solution of the test prodfate. The solvent wasre rno'ved in 'vacuo to give not were deposited on their ventral thoracic sur- 61 g. of the chlorination product of 1,1-diphenyl faces. Observations. of mortality were made 2,2-dimethyl-pr0pane in the form of a light yeldaily up to the end of 4 days. The results of low-colored oil. Fifty-one grams of this crude; these testsare indicated in table below:

TABLE insecticidal activity of halogenated diaryl neopentanes Clothes Moth Carpet Beetle Cockroach Milkweed Bug Percent Mor- Oompmmd Percent ercent A pplicaality Applica- Appliea- 122388, Applica. igging ti n, ,flon, hlzergelntt tion tion mg./kg or a 1 Y r Male ,Female Brominated diphenyl neopentane (crude oil) 0. 5 2. 7 0. 5 0. 2 2, 000 70 10 2, 000 Brominated diphenyl neopentane (32.5% Br,

B. P. 1647 0., at 1 mm 0.5 5.6 0. 5 1 -0 1 2,000 90 20 2,000 Bromine-ted diphenyl neopentane (40.8% Br, Y r V I i Y B. P. 183-7 C. at 1 mm,) 0.25 3.0 0. 25 0 2, 000. 90, 60 2,000 Chlorinated diphenyl neopentane (crude 011).... 0.5 1.0 0. 5 1. 6 2, 000 80 40 500 30 Chlorinated diphenyl neopentane (24.6% Cl, r Y B. P. 160-7 C. at 1 mm.) 0. 5 4. 8 0. 5 -1. 7 2, 000 70 2,000 50 Chlorinated diphenyl neopentane (27.9% Cl, 7 I

B. P. 167-9" 0. at 1 mm.) 0. 5 0.7 0.6 -1.e, 2,2918 7 1% 2,000

Chlorinated dipelmyl neopentane (32.3% Cl,

B- P. 174-87 C. at 1 mm.) 1.0 0 1.0 1.5 2, 000 0 2, 000 100 500 80 10 500 70 Untreated wool 80. 3 25, 4

Negative values due to unavoidable changes in humidity and larvae residue adheringto wool.

We claim:

1. An insecticidal composition comprising a halogenation product of 1,1-dipheny1-2,2-dimethyl-propane selected from the group consisting of the reaction product of the chlorination of 1,1-diphenyl-2,2-dimethy1-propane under conditions favoring ring substitution wherein the boiling point is between 160 C. and 187 C. at

pressure and the chlorine component does not exceed about 32.3% on a weight basis 3. An insecticidal composition comprising the reaction product of the bromination of 1,1-dipheny1-2,2-dimethy1-propane. under conditions favoring ring substitution wherein the boiling point is between 150 C. and 187 C. at 1 mm. pressure and the bromine component does not exceed 40.8% on a weight basis.

EDWARD F. ROGERS.

HORACE D. BROWN.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,455,643 Bakalar Dec. 7, 1948 2,487,854 Craig et a1 Nov. 15, 1949 OTHER REFERENCES Groggins,

Unit Processes in Organic Syntheses, page 169 (1947). v 

1. AN INSECTICIDAL COMPOSITION COMPRISING A HALOGENATION PRODUCT OF 1,1-DIPHENYL-2,2-DIMETHYL-PROPANE SELECTED FROM THE GROUP CONSISTING OF THE REACTION PRODUCT OF THE CHLORINATION OF 1,1-DIPHENYL-2,2-DIMETHYL-PROPANE UNDER CONDITIONS FAVORING RING SUBSTITUTION WHEREIN THE BOILING POINT IS BETWEEN 160* AND 187* C. AT 1 MM. PRESSURE AND THE CHLORINE COMPONENT DOES NOT EXCEED ABOUT 32.3% ON A WEIGHT BASIS AND THE REACTION PRODUCT OF THE BROMINATION OF 1,1DIPHENYL-2,2-DIMETHYL-PROPANE UNDER CONDITIONS FAVORING RING SUBSTITUTION WHEREIN THE BOILING POINT IS BETWEEN 150* C. AND 187* C. AT 1 MM. PRESSURE AND THE BROMINE COMPONENT DOES NOT EXCEED 40.8% ON A WEIGHT BASIS. 